Processes for breaking petroleum emulsions



patented Feb. 28, 1956 UNITED STA PROCESSES Melvin p'e Gm This invention. relates to processes or procedures particularlyadapted for preventing, breaking, or resolving emulsions of the water in-oil type, and particularly, petroleum emulsions. This application is a' continuation-in-part of our co-pending application Serial 'No. :666,819, filed May 2, 1946, now abandoned. See our co-pending application Serial No; 8,731, filed February 16, 1948. 1

Complementary to thej'above aspect of our invention is our companion invention concerned with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes [or procedures, as well asithe application of such chemicalc'ompounds, products, and the like, in various other arts and industries, along with methods for manufacturing said new chemical pmductifbompounds which are of outstanding value 'in* demiils'ification. See our co-pending application Serial No. 30,186, filed May 29, 1948. 1

: i LdQSfiSSJ j I V FOR BREAKING PE'rRoLEUM Y v ttei 'uiiiversitioita and Bernhard Keiser, Webster Groves, Moi, assignors to- Pet -rolite Corpo'ration','-"'Ltd., -Wilmington,-Del:,I a. corporation of Delaware No Drawing. Application Maiasfi 4s 7 Serial .0438 i Claims. (Cl. 252;s4 2) by the oxyethylation of 't; diglyeollic acid, etc.

certain acidic fra'c'tiona'l icih0leir'i.-- Such :acidic esters are obesters of 11* taiiied by-=ractirig triricinolein' with one to three moles of polycarboxy'-* acid and particularly a:

di'caiboxy aidE-JSuh-as phthalictacidg' adipic aci The hereto appended'claimsl. are limited to derivatives of dicarbox acids or id s.

Acidic esters-of triricinolein cantemanufactured in two different ways, although using the same:generalsprocedurerx ,One metho -ism 1 5.

: be attached to the glyc eryl radical and not limited Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type thatare commonly referred to as cut' oil, roily oil," emu1s ified oil, etc., and which comprise finendroplets of naturally-occurring waters or brinesdispersed in a more or less permanent statethroughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economcal and rapid process for separating emulsions which have been prepared under controlled conditions'froni minera1 oil, such as crude oil and relatively soft waters or weak brines.

mentioned are of significant value in removing impurities, particularly inorganic salts,'from\pipe= lineoil. a

Demulsification, as contemplated in the .present application, includes the preventive step of-scommingling the demulsifier with the aqueouscomponent which would or might-subsequentlybecome either-phase of the emulsion in the absence of such precautionary measure.- Similarly; such Controlled emulsification and sub sequent demulsification under the'conditionsjust 2 demulsifier may be mixed with the hydrocarbon to attachment to the ricinoleyl radical. This latn e of's ri ct r wi be p ar d bs quent: description It .is Y to, be noted, however, that, the compounds contemplated herein are those'obtained from intermediates in which the dicarboxy acid radical is attached tothe ricinoleyl radical, and thus excludes acidic esters obtained by rearrangement at highertemperatures or in presence of catalysts.

The manufacture of fractiona1 esters of tri-- ricinoleinis' well' linownand described in names ous patents.- The literature including variouspatents also describes the esterification of such fractional esters with polyhydric alcohols includ ing polyglycols under various conditions involving} for example, either the presence or absence of catalysts, or a variety of catalysts, including both acid andlbasiccatalysts. I

It has been suggested thatfl-thereactionf of a fractional ester with a polyethylene glycol under various conditions, would, in essence, result in a productsubstantially the same as that obtained by reacting with ethylene oxide so as to obtain the samestoichioinetric relationship. We have found that this is not the case and that the resultant products are significantly different in compositiomand those products obtained by oxyethylation are much more eiiective, for a number of purposes, such as, for example, demulsification of petroleum emulsions, break inducers, in the doctor treatment of sour hydrocarbons, etc.

Since this difference in composition involves the inherent nature of the reactants and resultants, it is deemed desirable to point out clearly the nature of the product obtained, when triricinolein is reacted with polycarboxy acids, and particularly those having 4 to 10 carbon atoms, and particularly dicarboxy acids having, 4to 8r carbon atoms, such asl'succinic acid, adipic'aacid;diglycol- 10 lic acid and phthalic acid. The anhydrides, of course, are the obvious equivalent of the acid ands include, among others, phthalic anhydride, maleic anhydride, citraconic anhydrideg etcz- Other suit-e 1 able acids include maleic, fumaric, oxalic, tricar ballic, tartaric, azelaic, sebacic,. ,etc., Qther. acids. include cisA-tetrahydrophthalic anhydride obftained by the action of butadie'na on.=maleic;anhydride, and 3,6-endomethyleneN-tetrahydrophthalic anhydride obtained by the ,action ot g, cyclopentadiene on maleic anhydride; It isltorbe; noted that none of these acids have more'tlian 10 carbon atoms.' As stated, it is understood that the acids and anhydr'ides are considered as equivalents I I 25 In preferred, esterproduct may, be 2 obtained by. esterification reactionbetween triricinoleinv and; aizdibasimcarboxylic acid, suchqas phthalic acid Riz'ziuoleicracid may; be indicated by, the following,

formula:

Triricinolein. readily esterifies:withphthalic-acid, 65

andz it ,three moles of. phthaliclan'hydrideioracid areicausedto: react with .one' m0le.of triricinolein, azafra'ctional, acidic ester will be obtainedaccords inggto; the followingreaction: o0

HORCOOCH coon: +=Hconooo na '-o.o ORG 0.0 on, 5

It is not necessary to use three moles of phthalic anhydride per mole of triricinolein, and if desired, one may use one or two moles, although the preference is to use approximately 2 to 2 or 3 moles.

Likewise, in carrying on the esterification reactions broadly, without limitation to the particular type herein employed as intermediates, it is not essential that a carboxylic group of the dibasic carboxylic, acid react with the alcoholiform'hydroxyltinithe ricinoleyl radical while the ricinoleyl radical remains directly connected with the polyhydric alcohol radical. One might react ricinoleic acid monophthalate, obtained by re- 1 action" between-.ricinoleic acid and phthalic anhydride, mole for mole, with glycerol, in the ratio of three moles of the fractional ester for one moleot' glycerol. This would yield a mixture of compounds, such :as the following:

HOOCROO HOTOfCROOO too noocizooo cooln 300g, coonco'o Hi.

,Not only may compounds. of the above type; be obtained: by; the procedure previously. described, butzsuch compoundszmay, occuri'to a greater or lesser: degree: as; the result f. of i'molecular rearrangement innthe r production: of acidic i fractional esters from 1 triricinoleinand various piolyearboxy acids, as previously mentioned, provided one employst L temperatures. in excess of: 1 2L0 C. orraemployss catalysts, or rboth'.v

In: carrying on the: esterification reaction; there may develop;- cross-linkages either: through: .the polyhydric Ialcoh'ohi orthrough the' polybasic :carboxylicv acid, due; to' the polyfunctionality of thesevmaterialss For example; 1112 anesterification reaction between triricinolein andnphthalic acid; theresulting-.zproductmay comprise :more complex.-molecules-,-such as the following, which illustrates crcsslinkage.Jzhroiigh the polyhydric alcohol residue.

HQCOOGROOJJ H H 000E005; COOH Ha OOCROOJJ gOORCOOCHi H OOCROOC CODE HaOOOCROO OORCOO H:

H OOCROOO OORCOOH Cross linkage, likewise, may occur through the polybasic carboxy acid to afiord molecular structure such as It is apparent that other cross linkages may occur. Such ester products containing morecomplex molecules are also suitable. It is also apparent that there may be great variations in the molecular weight of the product. The molecular weight'of, the ester product, as determined by cryoscopic methods, or from obvious composition'of the ester, usually runs between about 300 andabout 4,000 and is seldom over 6,000. Ester products having a molecular weight over about 10,000 preferably are not employed. During the esterification reaction there may be some polymerization and polymerized products, as well as simple monomers, may be used.

Attention is directed to what has been said previously for the sake of clarification and that is that the intermediates herein contemplated. i. e., the acidic esters derived by reaction between triricinolein and various dicarboxy acids or anhydrides, are limited to those obtained by manufacture under conditions which preclude drastic rearrangements, and thus are characterized by the fact that the dicarboxy acid radical is attached directly to the ricinoleyl radical and not to the glyceryl radical.

Tricarboxy acids may be employed as reactants one. phthalic acid, is employed, there is a single carever, it is obvious, in light of what is said subsequently, that if a tricarboxy acid is used, subsequent oxyethylation results in a branched chain or two chains of polyglycol radicals instead of In other words, if a dicarboxy acid, such as boxyl radical available for oxyethylation. If, on

the other hand, tricarballylic acid is employed, then there may be, and in most instances therehappens to be, two carboxyls available for oxyethylation, thus resulting in either a branched chain or two separate polyglycol radicals. Actually, the configuration so produced from a. structural standpoint, closely approximates that obtained by treating a sole carboxyl radical'remaining from phthalic acid with glycide or glycerol and then oxyethylating such ester so as to obtain a branched chain polyglycol or two separate polyglycol radicals. Since this type of compound is contemplated in our co-pending application Serial No. 30,187, filed May 29, 1948, it will be noted that the specific examples herein included and the claims themselves are directed to derivatives of dicarboxy acids.

TRIRICINOLEIN ACIDIC FRACTIONAL' ESTERS Example 1 One pound mole of triricinolein (in the form of 'castor oil which ordinarily contains approximately to triricinolein) is reacted with 2 pound moles of phthalic anhydride to produce a mixture of acid phthalates consisting essentially of triricinolein dibasic phthalate and triricinolein tribasic phthalate. The reaction may be caused to occur by heating the mixed materials at a temperature of approximately to C. for approximately, 6 to 12 hours. The action can be followed roughly by withdrawing a small sample of the partially reacted mass and permitting it to cool on a watch crystal. When the reaction has become completed no crystals of phthalic anhydride appear. When the sample no longer shows the presence of such crystals on cooling, it can be titrated with a standard volumetric alkaline solution, since the acid which remains is due entirely to carboxylic hydrogen in the fractional ester and not to any unrea'cted phthalic anhydride. If care is taken not to use too high temperatures which would cause formation of heterocyclic bodies of the character above referred to, one can depend upon the standard alkaline solution to indicate the disappearance of the phthalic anhydride. It is not to be inferred, however, that any cyclic bodies, if formed, would be unsuitable.

The product thus obtained, however, seems to consist largely of triricinolein dibasic phthalate and triricinolein tribasic phthalate. Apparently there is no evidence of rearrangement there. This fact is indicated by a molecular weight determination, and also based on the acid value,

which usually runs from a little over 100 to slight- 1y less than 110.

TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS Example 2 Maleic acid or anhydride is substituted for phthalic anhydride in preceding Example 1 to give the corresponding maleic acid derivative, 1. e., triricinolein dibasic maleate and triricinolein in the same manner as dicarboxy acids. How-J i5 tribasic maleate.

7*? rsmremonsm ACIDIG; 1 ERAG'IIONAL- ESTERS;

Adipic 7 acid. or, anhydride; is, substituted for phthalic anhydride .in preceding Example l tegive the, corresponding.- adipic acid derivative,v i. e, triricinolein dibasicr adipatei and triricinoleine tribasic adipate.

'IRIRZICINOLEIN* e'IDI c FRAcTioNAL' Y E Ezrample a Succinic" acid"'or anhydrid is substitutedi fforzf ph tha lioanhydride, in preceding"Examplef 1; to"

give, the corresponding. succinic" acid? derivative;

if e.', triri'cinolei'n dib asicsuccinate and triricino -r lein trib asic succinate.

It is: to; be cnotedxthat the triricinoleina acidic:

fractional .estersxherein contemplatedlxas ;the'.pre':-@: ferre'di reactants. are.- characterized iby'sthel: fact that they 4 are? obtained by. esterificationreactions involving the; use of s at; leastone mole 'ofsthe dica'rboxy acid per.:m*olewoigtriricinoleins- Eorinstance, previous formulael indicatei combinations" wherein 1V -.moles to Svm'oles of phthalicanhye' dride/ are used. per mole: of: triricinoleini In; all instances; regardless of the ratiorlof-sdicarboxm res a'ctant toitriricinolein', there mustibe ataleast ohe free carbo'xyl; per mole: of triricinolein in gthevfin ishedi product; Such requirementi is men ofcourse;: by triricinolein monobasic: phthalatel de-z-z rivedzfrom onemole of ltriricinol'ein andronermole, of .phthalic. anhydride. Attention is" also directed t'o/the facts that allthe: fractional. estersrarepre pared in such a manner: that the final pro ductl-is anhydrous. The next step is; theo bv-ious one; of subjecting 'suchanhydrous ester: to .the action 01 ethyleneroxides Ifilone examines the formula: for ricinoleic acid, it becomes. obvious that the dicarboxy acid; such as phthalic acid, becomes attached approximatelyshalf-wayin the carbon, atomchain, and thus oxyethylationattacking any residual carb'oxyl'group which ispart of the dicarboxy; acid radical, must, of'necessity, cause the hydrophile piolyglycol group; to enter-or-make' its effective ness'. felthalf-way 1 in the carbon. atomchain, .as differentiated with the introduction. of, a hydrophile group at the end of a carbonatom chain. For instance, when a high molal alcohol or a high molal acid is subjected to oxyethylation, obviously such hydrophile -effect is produced terminally and not at a mid-point. In this connection it is interesting to no'te" that oxyethylation do'esitnot; as one: timebelieved, attack the secondary alcohol of: triricinol'ein when. caster oilzis subjected to oxyethyl'ation. For this reason; oxyethylation of the. fractional: esters give a product having a hydrophobe-hydrophile balance,

which is entirely 'difierent from that obtained from a number of apparently kindred products. Generically speaking, oxyethylation is conducted in substantially the same manner as applied to a number of other products, in whiclr the ethylene 'oxide group is introduced between an oxygen lated so that it is used mp more or less uniformly atom and a hydrogen atom, as, for examplefln oxyethylation of high molal acids' or high molal alcohols, substituted phenols; etci Usually} a small amount of alkaline catalyst is added, such as one-tenth of 1% to 1% of caustic soda, sodium stearate, sodium methylate, or" the like. Oxyethylation is conducted with! constant stirring and ajgauge pressure of to 200 pounds per square inch is generally satisfactory. The temperatureof 'reaction may be varied from 100 C. to lss'than' 200"" If desired, an inert solvent may be present, such as xylene -tetralin, cymene, decalin, or the like. The ethylene oxide may be used continuously, provided the'aaddi'tion is reguas it enters the reaction vessel or autoclave. Our preference, however, is to add the material batchwise, as indicated, and continue" oxyethylation not only until the product =15- distinctly hydrophile, by until it gives a substantially clear solution in water. As to other oxyethylating procedure, attention is directed to" the following United States patents and tothe following British patent: U. S. Pat. Nos. 2,142,007, dated December 27; 1938 t'o- Pi sohlack 1 ,84-'5, 19&;.-.Eebruary': 16, 193 2, 0':- S'chmidt et ali; 1922,459;=Ai1gust 12,1.1933',v O. Schmidt et al.; British 302,041-,"-August7,'.1928}. Jas. Y. Johnson.

WATER-SOLUBLE OXYETHYDATED TRIRIC- INOLEIN ACIDIC FRAGTIGNAL ESTER Example 1 650 pounds of 'tri'ricinoleimacidic fractional ester manufacturedasdsoribed under the heading Example 1, preceding, is mixed with one-half pound of sodiummethylate'=and then reacted with approximately-'16]: pounds'of ethylene oxide in three batchesof 53.7 pounds, each. The maximum pressure during the reaction was pounds per square inch/ gauge. pressure. The time of reaction required foreach batch was three to five hours. The temperature employed was approximately. Ct. The; material. was tested for water: solubility, after the... addition .of 16. 1;. pounds of ethylene oxide, and. foundtoLbe watereinsoluble-a 117;, the theoretical molecular. weight-of; triricinolein tnibasic phthalate is cone, sidered; as. 1 150,: then the average. molecular. weight of the;raw material employed was taken as 1300. On. this :basis, theamormt ofJethylene oxide added; attthispoint represented .,a..molal ratiorof 1 -.to 7.3,.approximately. Oxyethylation was vthencOntinuedby the addition of three .moretportions of approximately 60 pounds eachz-so that-atthe end. of, the. sixth batch, the molecularratidhadQmorethan doue bled and wasapproximatelylto .18'I0l Tlieprodnot-at, thiswpoint began to, Show some l distinctly. hydrophile, character andLsolubility, but was re.- acted further with. five additional .portions of approximately ;65 pounds-each Thus, the .,t0.ta1 amount ;ofethylene. oxide added I represented l6 1 pounds plus pounds plus. 325: pounds, being a total-of, 666 pounds. of ethyleneoxide added to 650,-. pounds OfLthepriginaIT resins On. a weight basis, thisrepresented (slightly. in excessof 1 to 1, and on a molal'ibasisnit,represented;approxi mately 30 .to 32 moles ofiethylene oxide per mole 0L. monomeric, fractionalf estelz. The resultant l1 glycide or methylglycide instead of ethylene oxide or the like, or glycerol for that matter, then such esters are capable of attack by ethylene co-pending application Serial No. 666,820, filed May 2, 1946.

Products of value as demulsifying agents have been prepared by reacting triricinolein phthalates of the kind described under the heading Triricinolein acidic fractional esters with polyhydric alcohols, although not necessarily with polyethylene glycols having a large number of repetitious ether linkages in such proportion and manher as to render such fractional esters watersoluble or water-miscible. At first casual examination it would appear that if one were to react theacid phthalates, as exemplified by Triricinolein acidic fractional ester, Example 1 with polyethyleneglycol' representing approximately 10 or 12 ethylene oxide units, there should be obtained a product approximately identical with theproduct described under the heading Watersoluble oxyethylated triricinolein acidic fractional ester, Example 1. For instance, the reaction may be indicated in the following manner:

COOH

cooacooom COOROOO H:

COORCOOCH:

H(H4Cz),-OOC OORCOO E 311:0

COORCOOCH:

The above reaction emphasizes this very important feature, that if an attempt is made to polyethyleneglycol on the other, is this .particular situation; the esters employed-are polyf'unctional, having, for example, preferably two or more carboxyls per original molecule of triricinolein'. The polyethyleneglycols are difunctional. Thus, when reacted together, there is a tendency to form a sub-resinous polyester by reactions involving simultaneously one mole of a polyethylene glycol and two carboxyls, which are part of the same molecules or much more probable parts of two different molecules.

COOH

COORCOOCH1 COOH COORCOO H2 HZCOOCROOC COOH HOOOCROOO GOOH HQGOOCROO COORCOOCZH H(OOCROO& COORCOOH Hg GOOCROOC COORCOOH wherein HOC2H4XC2H4OH represents the original polyethyleneglycol.

In connection with what is said herein in regard to the difference between oxyethylation, on the one hand, and esterification, on the other hand, it must be remembered that oxyethylation takes place readily and rapidly at temperatures considerably under 200 C. and that this particular temperature may be considered the upper limit. Esterification, such as is shown subsequently, invariably involves much higher temperatures, such as 230 to 340 C.

An examination of such esterification reactions are best conducted on a laboratory scale. In other words, if one were to start with approximately 650 grams of the mixture described under the heading Triricinolein fractional ester, Example I having an acid value of approximately 105, and add thereto the equivalent of 2 moles of a polyethyleneglycol havin approximately 10 to 11 structural units on completion of reaction, one would anticipate that there would be a drop in acid value to approximately zero, corresponding to the acid value of the product described under the heading Water-soluble oxyethylated triricinolein fractional ester, along with the elimination of a stoichiometrical amount of water which would be equivalent to 2% moles or 17 grams.

Such reaction can be conducted in any one of three ways: (a) Absence of a catalyst; (b) presence of an acid catalyst, or (c) presence of abasic catalyst. Actually, there is little or no jus'tification for using a basic catalyst, for the reason that under such circumstances one would not expect to obtain a product comparable to that described under the headin Water-soluble oxyethylated triricinolein fractional ester, Example 1, but would expect to get a product in which a large degree of glycerol had been replaced by the nonaethyleneglycol with subsequent corresponding reaction. In other words, one would expect trans-esterification, which is sometimes referred to as ester-interchange or alcoholysis. (See Organic Chemistry, Fieser &: Fieser,' 1944, page 182; and Organic Chemistry, Fuson 8; Snyder, 1942, page 92.)

In conducting these exploratory experiments, it becomes obvious that the two end points did not coincide, i. e., the elimination of the theoretical amount of water of reaction and reduction of the acidity to the value of 1 or 2. In each instance, an attempt was made to carry'the reaction to the end point indicated in both ways, In the case of the acid catalyst /g% of paratoluene sulfonic acid was added. In connection with the polyethyleneglycol reactant attention is directed to the article entitled Technology of the Polyethyleneglycols and Carbowax Compounds (Chemical and Engineering News, volume 23, No. 3, page 247 (1945)). Such article points out, among other things, why the value of n, as herein contemplated, represents an average value, rather than an absolutely definite value of one single compound. The result of these experiments are indicated in the following table:

Experiment A1L-24142 Experiment B L-24l43 water which would be expected to be eliminated in experiments A, B and C so as to give a product identical with that previously referred to as Example 1, would be 17 /2 grams of water. Actually, when l'l' /z grams of water had been eliminated in all three cases, the acid value varied from approximately 20 to approximately 33. On the other hand, when the minimum acid value was obtained, even though it did not approach the amount of 2, there was a great deal more water eliminated than theory; varying from 54, in one instance, to 346 in the other. Furthermore, in order to obtain the result indicated, instead of using a temperature of approximately 130 C., or somewhat higher, but in any event, under 200 C., the temperature actually varied from 230 C. to 340 C. Attention is directed to a very significant fact, that is, that these temperatures employed in experiments A. B and C, as previously noted, vary from 230 C. to 340 C. and are Within the range which produces rearrangement in the manufacture of acidic esters, as previously noted. In other words, at such temperature range, even though no catalysts were added, one would expect rearrangements, whereby, at least to a substantial extent, there would be present compounds in which the dicarboxy acid radical would be directly attached to the glyceryl radical. It is to be noted that this type of material is specifically excluded in the hereto appended claims.

In light of what has been said as to the nature of the reactions taking place and as to the results obtained in the above experiments, it is perfectly obvious that there is a very marked difference in the nature of the products obtained, depending upon whether an acidic fractional Experiment 0 1 -24144 Triricllnolein Fractional Ester,

650 grams-Acid v.=l05

650 grams-Acid v.=105

HO (CrH4O)..H 700 grams 700 grams Catalyst Nnne 36% Toluene Sulionic Acid....

Acid Value of Mixture. 50.5. 52.0.

Oondigionszt-o bring acid value Could not get below 14. Could not get below 15.6

to 3 out Time. 3 ho r 4 ho r Maximum Temperature 340" C 300 C At this point H2O eliminated. 346 cc 66.8 cc. H20 and 53.4 cc. oil..

Acid value rose on further heating.

650 grams-Acid v.=l05.

700 grams.

23 7;, Sodium Methylate.

4 hours at 325 0. 7.35 acid value.

4 hours.

54 00.1110 and 15 cc. oil.

Acid value rose on further heat- Conditions to bring about elimination ofl7l gr. water (theoretical).

Time m 25 min hr.

Maximum Temperature 280 C 230 C 285 0.

Acid value at this point. 32.8. 36.6. 20.4.

Remarks. Clear oil; cloudy solution Clear oil: cloudy solution Clear oil; cloudy solution with with water. with water. water.

In comparision with experiments B and C,

it'has been pointed out previously indOxyethylated water-soluble triricinolein acidic fractional ester, Example 1 that such reactant -as was used in experiments A, B and C can be treated with v was approximately 2.

In examining experiments A, B and C, it is to be noted that it was impossible to reduce the acid value in any one of the three cases to that obtainable by oxyethylation, to witf a value of 2.

Actually, the values range from approximately 8 to 14. Furthermore, the theoretical amount of ester is subjectedto oxyethylation, .or whether it is subjected to an esterification with a polyglycol, in an effort to obtain substantially the same product; although, for the sake of brevity, reference is made only to products obtained by phthalation, actually other experiments conducted with other polycarboxy acids, particularly succinic acid, adipic acid, diglycollic acid, etc., indicate that results are substantially the same. The difference in the nature of the products obtained. by the two diiierent procedures, is illustrated further by their effect upon emulsions. The following table shows results obtained by adding an equal amount of the same four materials to certain emulsions. One demulsifying agent consists of the product described under the heading Water-soluble .oxyethylated triricinolein acidic fractional ester, Example 1. The other three consist ofthe clear oils obtained as anemone titstesultants ifrom :experiments .B rand WC, ide- .'.scribed previously; intabular. form. Here 1 again, Jtlis to-zbemoted that,=:althoughatheanesults :indi- .cated rare concerned with .imerely one particular iderivative, i. e., phthal-icacid derivatives; the .re- .--sults:.are thewsame,'as farras demulsificationiwhen rotheripolycarboxy acid derivatives are examined tthe same way. :Thisisgparticularlytrueuof adipic acid,=.-succinic' acid;diglycollic acid. etc.

.ilttmayrbeidesirable to point outfthat. distillable .ipolyglycols. of 'therkindpreviouslyreferred .to and sexemplified by nonaethyleneglycol vor .thelike, zandrparticularly thosezhaving 8 to. l2toxyalkylated egroups, are ksometimesreferredio. as :upper distfllableaethyleneglycolst l(-S'ee U. vS. Patent No. ;2,32;489,tdated 1July' 20,. .19!l3, to De Grooteand Keise'rr) rAlthough .itz'has :beentold :to :rsubj ecteemu-lsions etoiiem'ulsifying agents obtained by reaction Joe- =tween :certain :resinous products and polyhydric alcohols:free"ifrom'repetitious ether: linkages; yet, asfar'tas' we are:aware, products'of the-.kind.-.-.exie'emplifiedby :eXperiments1A, Band C have 'not tbeeniihereto preparedtor employed-as demulsifying agents.

.DEMULSIFYING'TEST NO. '1

JDate'Gf test--- 0017.530; 1.945

State of .Galifornia l'Oil field LOak Canyon Oil company V...'B.' .Wickham iLease No.14

-'We'll No *4 Percent emulsion in fluid from Nature of agitation; -machine with shaker arm; shakes .aper

minute .130 Ratio of demulsifier to wellfiuidl "156700 -Well No.

.DEMULSIFYING TEST NO. .12

JDateof .tes't- Dec. .13, 19.45 *State of California :oil field Wilmington Royalty Service Santa Fe B-'2 ;.Oil .:companyw Percentemulsion ini fluid from :iEencentzfree waterinifluid; from fplete demulsification. 1.18.0

.Rercentdemulsifier.in.test.solu- .tion .2 .Temperatureof tests 160 C. Period of agitationaf-ter adding .Nature of .agitation; machine with i shaker arm; shakes per .minute .130 .Ratio 10f demulsifier to well fluid.-- 115000 b24142 L-24143 L-24144 L-12866 Blank Time "IestLStarted 10150 1 cc. Water out at- '2 Trace. 1 8 .Do. 1 .11 ;D0. 2 4 '14 .Do. 4:30 a s 4 :14' E'Do. #mosueam- 5 -14. s .14 1130. "9.10 (12-7) 9 's 7 15 CD0.

DEMULSIFYING TEST NO. '3

"Daterif test Dec. 13,.194'5 State-of California Oilfield Wilmington Oilcompany Royalty'Service .Lease Santa "Fe Well No.. B-1 IIPercent emulsion in.fiui'd "from .well 2410 Percent .free.wateninffluidJfrom well 0.3 Percent water obtained by complete demulsification 22.0 vPercent demulsifier in test solution 2 "Temperature of 'tests 160C. 'Period of agitation after adding demulsifier 5min. Nature of agitation; machine with shaker armpshakes per minute 130 Ratio of demulsifier to well "fluid (1:5000

3L24142 L-24143 1,-24144 b12866 IfBlank -Time Teststarted,

cc. Water out at- 1:25 (1213) "Trace Trace Trace '8 'LTrace. 1:45 i 2 Trace Trace .13 .Do. 5:00.. '3 1. Trace 14 Do. 8:35'(12 6 '2 3 :15 CD0. 4:50 '7 3 4 17 Do. 12:05 "7 '2 5 '17 Do. 101002-17) :11 a s 19 .130.

Q It;is .zof considerable interest -to compare.;com-

j, pounds :of [the kind .herein described with 5 some- ;what "analogous compounds described elsewhere .in the literature vorprepared from .data appearlcbu'ildingmlocks :ors'structural units -.which;can l'be .fitte'd:together tq givevarious compounds. Castor oi1 ;(triricinolein) .maybe consideredaas.ricinoleic :acidzandjiglycerol incombination.

Some such other structures may be exemplified by examples which appear in the series of U. S. Patents Nos. 2,295,163 through 2,295,170, incluated acid ester, alcoholysis can and usually does take place, particularly at elevated temperatures. This is not true in the case of ethylene oxide.

Per cent phthalyl Identif radical final fi c ei l Per cent lng NUZI- oleyl Pmdu" iesidue cmio be: oi" Reactants and how made radical O O in final radicals Com- (RC)1 in H H product in final pound line. product product (OaHs) L-24633. Castor oil plus 2% moles phth. enhyd. (135 C.) to give acid 33. 2 12.0 1. 75 51. 5

ester plus EthyleneOxido (140 0.).

L24645 Castor oil plus 2% moles phth. anhyd. plus polyglycol 32.4 11.7 1.70 53.7

L24646 Polyglycol M. W. 1540 .8 mole plus phthalic anhyd. 1.6 31.2 13.1 1. 64 52.8

mol plus castor oil .8. The polyglycol plus anhyd. heated until acid v. drops to it ol orig. The castor oil is added and heated again for 2 hrs. at 250 C.

L-24650- Castor oil plus 2%: moles phth. anhyd. (135 0.) plus 31.4 11.3 1.65 53.1

polyglycol 770.

sive, all dated September 8, 1942, to De Groote and Keiser. Briefly stated, a polyglycol acid ester such as nonaethyleneglycol dihydrogen dimaleate, or dihydrogen diphthalate, obtained by reaction between one mole of nonaethyleneglycol and two moles of an appropriate dicarboxy acid or anhydride, is reacted with various hydroxylated compounds, including triricinolein, diricinolein, monoricinolein, etc.

The following table briefly describes four such compounds, the first being an ethylene oxide compound of the kind herein specified. In the next three compounds, or products, an ethylene polyglycol is used instead of ethylene oxide. The compounds were prepared in an efiort to have the ultimate composition of the last three compounds approximate with, or identical to, that of the first compound, in terms of structural units.

Needless to say, as has been pointed out already, such resemblance is only superficial for the reason that, depending on the temperature of reaction, order in which reactants are added, and the very nature of the possible reactions themselves, one does obtain products which are inherently and intrinsically difierent in molecular structure, size of molecule, etc.

It is well to recall that the use of compounds of the kind herein described for the purposes involving surface activity, particularly demulsification, does not involve chemical reactivity in the ordinary sense. Surface activity, and particularly surface activity phenomena as exemplified by demulsification, is concerned with the actual shapes and sizes of molecules. Such concept, even though obscure and difficult to define, acquires a large degree of reality and Value in an invention of the kind herein specified even though it is difficult to set forth such qualities in measures which are more concise and specific than those which have been included.

Only a few examples need be repeated at this point to emphasize these difierences which, in our opinion, are related to the sizes, shapes, and association of molecules, and especially at interfaces. If phthalated castor oil is reacted with ethylene oxide, one builds up a derivative of the type in which there is always a residual hydroxyl for the reason that ethylene oxide acts like a monofunctional reactant. If one substitutes a glycol for ethylene oxide, then one is employing a difunctional reactant, and one mole of a glycol can act as a coupling reagent to unit two moles of phthalated castor oil. Likewise, with the glycol and a glyceride, or any ester including a phthal- In examining the above table it will be noted all radicals shown do not add to quite 100%. The reason is that some connective oxygen atoms are not included, particularly those attached to glycerol and that, in some instances, there may have been elimination of water which alTected the final percentage.

Attention is directed to the fact again that L-24633 typifies one of the compounds described herein. In L-24645 the same intermediate (phthalated castor oil) Was reacted with a polyethlyeneglycol having a molecular weight of 1540, so as to give a compound which is analogous as far as its structural parts are concerned, as in the case of L-24633. In L-246l6 the polyglycol was first combined with a phthalic anhydride and reacted with a castor oil in a manner described in the series of patents previously referred to, to wit, U. S. Patents Nos. 2,295,163 through 2,295,170. In compound L-24650 the procedure was substantially the same as in L-24645, to wit, the intermediate was the same as in 11-24633 (phthalated castor oil), but instead of using a mole of a polyethyleneglycol having a molecular weight of 1540, there was used instead two moles of polyethyleneglycol having a molecular weight of 770.

In addition to the four compounds above described, i. e., one derived by the use of ethylene oxide and the others by the use of a polyethyleneglycol, it is obvious that other compounds could be made, including the use of alkoXy polyethyleneglycol. For instance, one could introduce a residue from a monohydric alcohol, such as methyl alcohol, ethyl alcohol, or propyl alcohol, etc., into a glycol. Such alkyl radical is introduced rather easily by simply substituting the monohydric alkyl ether of a glycol for the dihydric glycol. A suitable compound could be obtained by treating methyl or ethyl alcohol with ethylene oxide so as to give an ether glycol having a single hydroxyl and a molecular weight comparable to the molecular weight of the glycol previously described, that is, 7'70 and 1540.

However, removing a terminal hydroxyl radical prevents association and produces all sorts of changes which difierentiate derivatives of alkoxy I. polyethyleneglycols from the corresponding de- As to compounds or mixtures involving the use of alkoxy polyethyleneglycol plus castor oil and a dicarbozgy acid, see .11. S. Patent No. 2,081,266, dated May 25, 1937, to Bruson. Compounds of this type, when compared with L-24633, 'do not show nearly the comparative effectiveness as a demulsifier, or for other purposes, such as use as a break inducer in the treatment of sour hydro- Per cent water obtained by complete demu'lsiflcation Per cent demulsifier in test solution Temperature of tests 90 F. Period of agitation after acid- ...;L- Nature of agitation; ma-

Per. cent water obtained by ncomplete demulsification 44 Percent demulsifier in test ,solution T 2.5% Temperat'urefof tests 90 F. Period of agitation after F Nature of'agitation; machine with jshak er arm; shakes carbons 40 91 11. wifi she e arm; Th W om d w e fi t d a; Rgg gz amig m l iq vn numb typical emulsions F 7 .71 000 Some of the tests are as follows. (see-below) L- 2463 b24645 1 24646. L-zl'eta' reroent Demulsifier 2 s,opo /isjooo 'i isgboo, mom Blank Time fest started, 1:50 Q

stas '8' 7 T s'40 4 2 F22 E24 212 '22 15%? 440 4 2 26 521 26 26 Do. 121 0 1 2 31 2s .23 .30 no 1o;50(4/3 1 2s 28 an no. 1=oo (414).... 32 -31 31 31 Do.

DEMUL SIFY'I'NG TEST No. 4 51d "J L slFYinIG'TEsT No. 6 Date of test l April 2, 1948 Dateof testnln; Apr.-2,1948 .Statejof .a California State -or California Oil field Montebello Oil field; Seal Beach .011 company Century 'Oil company Hellman Estates 'Ljease Repetto L'ease: 8A Well -l No.15 Well "3A Per Ce emulsion in fluid Per cent emulsionin fluid from well 59 40 from wel1 l; my. 20 Percent water in fluid from Per cent free water'in fluid w ll l 3 from well'. 6

Per cent waterobtain'ed by complete demulsificatiom. '16

Nature of agitation; ma-

chine withshake'r arm;

1120,000 (next page) auctions L-24633 b24645 L-24646 L-24650 Percent Demulsifler 1/20,000 1110,000 1/10,000 1/10,000 Blank Time test started, :20 cc. water out at- 1 (4/ 10 10 8 8 Trace.

(4/ 12 11 10 11 D0. (4 13 ll 11 12 Do. 10 40 (4/3) 13 12 11. 12 Do. (4 1s 13 1s- 13 Do.

In addition to the foregoing demulsifying tests, the same four compounds identified as 13-24633, 11-24645, L-24646 and L-24650, have been tested on other emulsions with comparable differences. For sake of brevitythese other testsare omitted but they include, among others, a test, on an oil from Well No. 16, Cueller Lease of Cox and Ham-'- mond, in the HofimanPool, Alice, Texas; the Stanolind Oil & Gas Company composite sample from the battery from a lease located in'the Wink Field near Kermit, Texas, etc.

These series of tests reveal that the compound obtained by the use of ethylene oxide was 35% to 65% better in numerous instances, and not 'infrequently was 100% better.

What has been said previously in regard to the structure of compounds which appear to be analogous at first superficial examination, should be reconsidered in light of the previous descripwith the industrial application, as for instance,

break induction in doctor treatment of sour hydrocarbons. The fact that there is a similarity, in fact, almost an identity of structure when measured in terms of acid radicals, ethylene'oxide radicals, etc., does not mean that the size of molecules is the same for the obvious reason that the same materials of construction yield architecturally different products.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly. aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil,carbon tetrachloride, and sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents, customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may beused alone, or in admixture with other suitable well known classes of demulsifying agents.

It is well known that conventional demulsiiying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form which exhibits both oil and water-solubility.. Sometimes they may be used in a form which exhibits relatively limited oil solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, or even 1 to 40,000, or 1' to 50,000, in desalting practice; such an apparent insolubility in" oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

We desire to point out that the superiority of the reagent or demulsifying agent contemplated in our process is based upon its ability to treat certain emulsions more advantageously and at somewhat lower cost than is possiblewith other available demulsifiers, or conventional m1xtures thereof. It is believed that the particular demulsiiying agent or treating agent herein described will find comparatively limited application, as far as the majority of oil field emulsions are concerned; but we have found that such a demulsiiying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practising our process for resolving petroleum emulsions of the water-in-oil type, a treating-agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

The demulsifier herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, 1. e., bringing the demulsifier in contact with the fiuids of the well at the bottom of the' well, or at some point prior to the :emergence of said fluids. This particular type of application is decidedly feasible whenthe demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially ifsuspended in or dissolved in the acid employed for acidification.

A somewhat analogous use of our demulsifying agent is the removal of a residual mud sheath which remains after drilling a well by the rotary method. Sometimes the drilling mud contains added calcium carbonate or the like to render the mud susceptible to reaction with hydrochloric acid or the like, and thus expedite its removal. One preferred and more narrow aspect of our invention, insofar as its is concerned with demul-sification of petroleum emulsions of the waterin'-oil type, is concerned with the admixture of the ester, as described, with a viscosity-reducing solvent, such as the various solvents enumerated, particularly aromatic solvents, alcohols, either a1- cohols, etc., as previously specified. The word solvent is used in this sense to refer to the mixture, if more than one solvent is employed, and generally speaking, it is our preference to employ'the demulsifier in a form representing 25% to demulsifier and'15% to 75% solvent, largely,-'if not entirelynon-aqueous, and so selected as to give a solution or mixture particularly adaptable for proportional pumps or other meas- DEMULSIFIER Example 1 Per cent Oxyalkylated water-soluble triricinolein fractional ester, Example 1 60 Xylene 20 Isopropyl alcohol 20 DEMUL SiFIER.

Example 2 Per cent Oxyalkylated water-soluble triricinolein tractional ester, Example 4 '70 Cresylic acid 20 Normal butyl alcohol -10 DEMULSIFIER.

Example 3 v Per cent Oxyalkylated water-soluble triricinolein fractional ester, Example 4 70 Aromatic petroleum solvent l0 Isobutyl alcohol -Q. l0 Acetone 10 DEMULS IFIER Example 4 Per cent Oxyalkylated water-soluble triricinolein fractional ester, Example 4 65 Methyl alcohol 15 Di'chloroethylether 20 In the hereto appended claims the Word watermiscible is employed to designate a sol or solution which is permanent for either an indefinite period of time, or for such extended period of time as would unquestionably permit its utilization for the herein designated purposes without undue difficulties.

' The products herein described, and employed as demulsifying agents in our process, may be considered as intermediates for further reaction. For example, they may be reacted with chloroacetic acid or similar low molal alpha-halogenated carboxy acid to produce an ester. Such ester will serve many of the purposes herein described, i. e., as a demulsi'fier, break inducer, etc. Such alpha-halogenated carboxy acid ester may be reacted further, for example, with a'tertiar'y amine, such as dimethyldodecylamine, esterified.

triethanolamine, in which the acyl radical is derived from a detergent-forming monocarboxy acid, and from hydroxylated amines obtained, for example, by reaction with high molal amines, such as octadecylamine with two moles of ethylene oxide. Such compounds or derivatives again can be employed for all of the various purposes herein indicated, and particularly for demulsifi cation.

The wordmiscible is frequently used to mean soluble in all proportions. In a technical sense it is sometimes employed to mean soluble without necessarily meaning in all proportions, and such solubility may include a colloidal dispersion or sol as well as molecular solution. The word water-miscible is employed in the hereto appended claims in this more restricted meaning. Having thus described our invention, what we claim as new and desire. to secure. by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a water-miscible oxyethylated triricinolein acidic ester; said triricinolein'acidic ester being that of a saturated dicarboxy acid having not over 10 carbon atoms and characterized by the fact that prior to oxyethylation there is present at least one dicarboxy acid carboxyl radical for each triricinolein, and all dicarb'oxy acid radicals are directly attached to the ricinoleylradical, and with the further proviso that the w'eight'of ethylene oxide added by reaction based on the weight of the triricinolein acidic ester prior to oxyethylation is within the range of"75% to%.

2. A process fox-breaking petroleum emulsions of'th'e' water-in-"oil type, characterized by subjecting the emulsion to the action of a demulsifier including a water-miscible oxyethylated triricinolein acidic ester; said triricinolein acidic ester 'beingthat of a saturated dicarboxy acid having not over 10 carbon atoms and characterized by the fact'that prior to oxyethylation there is present a plurality of dicarboxy acid carboxyl radicals for each triricinolein radical, and all dicarboxy radicals are directly attached to the ricinoleyl radical; with the further proviso that the weight of ethylene oxide added by reaction based on the weight or the triricinolein acidic ester prior to oxyethylation is Within the range of 75% to 125%. a

3. A process for breaking petroleumemulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a water-miscible triricinolein acidic ester; said triricinolein acidic ester being that of phthalic acid and characterized by the fact that prior to oxyethylation there is present a. plurality of phthalic acid radicals for each triricinolein radical, and all phthalic acid ralicals are directly attached to the ricinoleyl radical; with the further proviso that the weight of ethylene oxide added by reaction based on the weight of the triricinolein acidic ester prior to oxyethylationis within the range of 75% to 125%.

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by sub- .iecting the emulsion to the action of a demulsifier including a water-miscible triricinolein acidic ester; said triricinolein acidic ester being that of adipic acid and characterized by the fact that prior to oxyethylation there is present a plurality of adipic acidv radicals for each triricinolein radical, and all adipic acid radicals are directly attached. to the ricinoleyl radical; with the further proviso that the weight of ethylene oxide added by reaction based on the weight of the triricinolein acidic ester prior to oxyethylationis withinv the range of 75% to 125%.

5. A process for breaking petroleum emulsions of the wate'r-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier including a water-miscible triricinolein acid ester; said triricinolein acidic ester being that of a diglycollic acid and characterized by the fact that prior to oxyethylation there is present a-plurality of diglycollic acid radicals for each triricinolein radical, and all diglycollic acid radicals are directly attached to the ricinoleyl radical with the further proviso that the weight 01' ethylene oxide added by reaction based on the 25 weight of the trlricinolein acidic ester prior to oxyethylation is within the range of 75% to 125%.

MELVIN DE GROOTE.

BERNI-IARD KEISER.

REFERENCES CITED The following references are of record in the file of this patent:

Number 26 UNITED STATES PATENTS Name Date De Groote et a1. Apr. 28, 1942 De Groote et a1 Sept. 8, 1942 De Groote et a1. Sept. 8, 1942 Moeller Jan. 5, 1943 De Groote et a1. Mar. 28, 1944 De Groote et a1. July 18, 1944 De Groote et a1. Ma 25, 1948 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTIOIN OF A DEMULSIFIER INCLUDING A WATER-MISCIBLE OXYETHYLATED TRIRICINOLEIN ACIDIC ESTER; SAID TRITRICINOLEIN ACIDIC ESTER BEING THAT OF A SATURATED DICARBOXY ACID HAVING NOT OVER 10 CARBON ATOMS AND CHARACTERIZED BY THE FACT THAT PRIOR TO THE OXYETHYLATION THERE IS PRESENT AT LEAST ONE DICARBOXY ACID CARBOXYL RADICAL FOR EACH TRIRICINOLEIN, AND ALL DICARBOXY ACID RADICALS ARE DIRECTLY ATTACHED TO THE RICINOLEYL RADICAL, AND WITH THE FURTHER PROVISO THAT THE WEIGHT OF ETHYLENE OXIDE ADDED BY REACTION BASED ON THE WEIGHT OF THE TRIRICINOLEIN ACIDIC ESTER PRIOR TO OXYETHYLATION IS WITHIN THE RANGE OF 75% TO 125%. 